Poly(1,2-divinyl ethylene oxide)-n2f4 adduct



United States Patent 3,433,776 POLY(l,2-DIVINYL ETHYLENE OXIDE)- N F ADDUCT Anthony J. Passanuante, Metucheu, and Eugene L.

Stogryn, Fords, N.J., assignors to Esso Research 3,433,776 Patented Mar. 18, 1969 ice EXAMPLE 1 Preparation of 1,2-divinyl ethylene oxide 5 a Eng neering Company, a corporation of g ig gg g g eggg t f g g g g e aware 2 a No Drawing. Filed Aug. 22, 1962, Ser. No. 219,373 and 41.6 grams of calcium chloride was added 190 grams U.S. Cl. 26088.3 5 Claims of acetyl chloride over a period of 45 minutes. During the Int. Cl. C081 15/04 course of addition, the reaction mixture was maintained This invention relates to a novel polyether of high NF ai fsg gfigifi sfiigfi fif g gfi i; 32 22 3 2 2?" 9 5 2; grepared by reacting polyuz'dlvinyl ethyl Oxlde) was continued for 2% to 48 hours it the end the reafi Wlt 2 4. o

tion mixture was warmed to 50 C. for 1 hour The reac- The novel poly(1,2-d1v1nyl ethylene ox1de)-N F adduct has a novel structure and a distinctively high N5 15 e g: 252 332 $31 52; vg flf g ggifirzgg fg i gg z g if to have the structure represented y solution of sodium bicarbonate. The ether layer was dried g over anhydrous potassium carbonate, filtered, and the ether removed by distillation. In this fashion, there was CHNFZ CHNFZ obtained 269' grams of the crude chloroester, 3-chloro 4- CIHZNFZ CH2NF2 acetoxy 1,5-hexadiene It is to be noted that this modified polymer of 1,2-divinyl ethylene oxide has in each monomer unit, 4 NR, oxidizing CHZICH'CHCI'CH(OOCCH -CH:CH groups per 6 carbon atoms and, on complete saturation can have l? to & Percent of content: The chloroester was converted to divinyl ethylene oxide the monomer Thls l of polyefher W1t h termmal by adding 257 grams of the crude chloroester product, dehydrolfyl E P 15 useful In the formatlon of P scribed above, dropwise to a stirred mixture of 362 grams mer b q a solld rocket Pfopenant comPOslte by of sodium hydroxide, 362 grams of potassium hydroxide, crosslmklng, elther to be made lnto acrylates or polyand 362 grams of Water heated to by a sand bath acrylates- The divinyl ethylene product was flashed over into a Methods Preparmg unsaturated epoxlde P' collection vessel by maintaining a slight vacuum 0n the mer, 1,;-div1nyl ethylene oxide, and the polymer are system. Approximately 80 ml. of crude epoxide Was colclosed appllcatlon 219,368 filed 22, lected in this fashion. Distillation of the crude product 1962, now US. Patent No. 3,261,819. yielded g. of divinyl ethylene oxide, boiling point Briefly, to pre pare 1,2-d1v1nyl ethylene oxide, 3, 108 to 110 C., a 21% yield based on 3,4-dihydroxy 1,5- droxy 1,5-hexad1ene is reacted with acetyl chloride in the hexadiene presence of calcium chloride to produce the chloroester, To obtain the polymers of 1,2 divinyl ethylene oxide 'F l' Libexadlene, ,Whlch then reacted monomer, this monomer is polymerized at a reaction temwith alkali hydroxide. These reactlons are shown by the 40 perature in the range of about 0 to C, preferably in followmg equatlons: the presence of an epoxide polymerization catalyst in the (H) C 01 amount of about 0.1 to 10% by weight of the epoxide a CHQ=CHCHCH-CH=CHZ CHaCOl monomer- OH OH CHZIOH CH CH CH=CH2 Polymerization of 1,2-d1vinyl ethylene mode 0 u Table I, given below, serves to illustrate the catalysts 1 O CCH that one can utilize for the polymerization of 1,2-divinyl K0H Na0H ethylene oxide to yield either low molecular Weight polymer or high molecular weight polymers. This table only CH2=CH CH CH CH=CH, serves to illustrate the catalyst that can be utilized for this epoxide polymerization and 15 not intended to be restrictive. More details are given in the following description.

TABLE I Monomer Catalyst ('(lliamsra Temperature Properties Divinyl ethylene PF5.THF 1 3 Ambient... Pale yellow solid. n i Al(i-Bu)3.H2O 2 -.do Yellow solid plus viscous liquid. Do NaOCHa 3 C Viscous liquid. Do PF5 3 Ambient Do. Divinyl ethylene PFs 8 do Do.

oxide plus H2O (9:1

molar ratio) The polymer obtained in these experiments are unsaturated polyethers, viz. they contain a polyethylene oxide chain with a substituent vinyl group on each carbon in the polymer chain, as represented in the following formula of the recurring unit:

This structure is confirmed by the infrared spectra of the polymers. These polymers contain appreciable hydroxyl functionality which can be utilized in the preparation of polyurethanes and acrylate derivatives useful as synthetic rubbers, textile sizes, etc.

The recurring unit will be present in the polymer a number of times, e.g., 2 upwards to about 100 or more, depending on the molecular weight, which in turn depends on the purity of the divinyl ethylene oxide monomer, the catalyst, and polymerization conditions. The

molecular weight of the polymers may vary in the range of about 200 to about 10,000 and higher. The preferred polymers used for the reaction with N 12, have an average of 3 to 30 units and molecular weights in the range of about 300 to 4000.

The following examples illustrate conditions of the polymerization reaction which has been summarized in the preceding Table I.

EXAMPLE 2 To 10 parts by weight of the divinyl ethylene oxide, prepared as described in Example 1, is added 1 part of phosphorus pentafiuoride-tetrahydrofuran complex. The monomer and catalyst mixture is stirred and maintained at ambient or room temperature (20 to 30 C.) for 3 days to form a pale yellow solid polymer having the recurring unit described.

EXAMPLE 3 The divinyl ethylene oxide monomer is polymerized with 10% of the triisobutyl aluminum-water catalyst (prepared by treating one mole of Al(i-Bu) in n-heptane with one mole of H The polymerization was carried out over a period of 2 days at ambient temperature to form a polymer product which is a yellow solid and viscous liquid.

EXAMPLE 4 The divinyl ethylene oxide monomer mixed with of sodium methylate reacts in 3 days at a polymerization temperature of 100 C. to form a viscous liquid having the desired composition.

EXAMPLE 5 In a mixture of the divinyl ethylene oxide monomer with water in a 9:1 molar ratio, 0.5% of the PF catalyst is used for the polymerization over a period ranging up to 3 days at room temperature to form the desired viscous liquid polymer.

The OH functionality of these polyethers can be increased by polymerization of the divinyl ethylene oxide in the presence of an OH-containing modifier, such as water, ethylene glycol, trimethylol propane, glycerol, and pentaerythritol. For example, the water-modified polyether described in the above examples has appreciably higher OH content than the corresponding polyether which was prepared in the absence of water. In general, the polyethers may contain 1 to 4 OH groups per molecule, but usually the polyethers contain on an average about 2 OH groups per molecule.

Preferably, 0.5 to 2 wt. percent of catalyst, based on the monomer, is used. The polymerization temperature may be varied from about 0 to 150 C. It may not be necessary to employ solvents or diluents in the polymerization, but inert solvents or diluents, or those which act as modifiers, maybe used in the polymerization.

The preferred method of this reaction involves the use of a chloro alkane solvent, such as a C to C alkane having 2 to 3 Cl substituent atoms per molecule, as in 1,2-di chloro ethane, di and trichloro propanes, CHCl and CH Cl Poly(divinyl ethylene oxide)-N F adducts Poly(divinyl ethylene oxide)-N F., adducts have been prepared successfully by addition reaction with N F in a halohydrocarbon solvent solution with moderate temperaturcs in the range of about 60 to 150 C. The adductsproducts have been obtained with an NF content in the range of 60 to 68 wt. percent, and in various states ranging from viscous liquids to solids.

The solvent used in the reaction preferably dissolves the reactants and the modified polymer product. Suflicient N F is used to react with the double bonds of the polymer, e.g., about 2 to 10 N m/monomer units.

EXAMPLE 6 Poly(divinyl ethylene oxide) dissolved in methylene chloride was reacted with N F in a proportion of 6 moles of N F per monomeric unit for about 8 hrs. at 100 C. in a glass pressure vessel. The resulting liquid reaction product mixture was degassed and filtered to remove a small amount of insoluble material which had formed. The solvent was evaporated from the resulting product solution to yield a yellow stringy solid that was easily soluble in methylene chloride. Analyses were obtained of the polymer indicating that the reaction tended toward complete saturation of the double bonds in the two pendant vinyl groups present in each of the recurring units.

TABLE II.POLY(DIVINYL ETHYLENE OXIDE)- N F ADDUCT 3 oxide] represented as:

(|3H0- H CHNFz l CHzNFg The recurring units are joined together a number of times, signified by the subscrip n which is in the range of about 3 upwards to about or more, depending on the polymer or fraction of polymer used as the oly(divinyl ethylene oxide) reactant.

Evaluations have indicated that the poly(divinyl ethylene oxide)-N F adduct is one of the best potential binders prepared up until now. A typical formulation for which a specific impulse of about 290 has been determined would contain 20 wt. percent of the polyether having the recurring unit [C H O(NF as binder with wt. percent of the liquid oxidizer and plasticizer tetrakis (NF butane, 26.5 wt. percent hydrazinium nitroformate, and 3.5 wt. percent boron powder as fuel. The liquid fluorine oxidizer component may be varied in composition and proportion. For instance, it may be partly or fully replaced by other liquid organic NF -containing compounds. The liquid NF -containing oxidizer can be decreased in proportion as the solid nitroformate is increased. Other types of oxidizers and other types of powdered metal fuels may be used.

What is claimed is:

1. Poly(1,2-divinyl ethylene oxide)-N F adduct containing about to 68 wt. percent NF 2. Poly [1,2,5,6,-tetrakis-(NF )-hexene-3- oxide] having the structural formula:

5 the subscript n signifying about 3 to 30 of the recurring units.

3. Method of preparing poly(1,2-'diviny1 ethylene oxide)-N F adduct, which comprises reacting poly(1,2-

divinyl ethylene oxide) with N F at about 60 to 150 5 C. and recovering the resulting N F adduct.

4. Method of claim 3 in which the poly(1,2-diviny1 ethylene oxide reactant and N F adduct product are dissolved in the same inert liquid organic solvent.

5. Method of claim 4 in which said solvent is a chloro 

1. POLY(1,2-DIVINYL ETHYLENE OXIDE)-N2F4 ADDUCT CONTAINING ABOUT 60 TO 68 WT. PERCENT NF2. 